The present invention relates to metallic glass alloys for use at high frequencies and the magnetic components obtained therewith.
Metallic glass alloys (amorphous metal alloys or metallic glasses) have been disclosed in U.S. Pat. No. 3,856,513, issued Dec. 24, 1974 to H. S. Chen et al. (The xe2x80x9c""513 Patentxe2x80x9d) These alloys include compositions having the formula MaYbZc, where M is a metal selected from the group consisting of iron, nickel, cobalt, vanadium and chromium, Y is an element selected from the group consisting of phosphorus, boron and carbon and Z is an element selected from the group consisting of aluminum, silicon, tin, germanium, indium, antimony and beryllium, xe2x80x9caxe2x80x9d ranges from about 60 to 90 atom percent, xe2x80x9cbxe2x80x9d ranges from about 10 to 30 atom percent and xe2x80x9ccxe2x80x9d ranges from about 0.1 to 15 atom percent. Also disclosed are metallic glass wires having the formula TiXj, where T is at least one transition metal and X is an element selected from the group consisting of phosphorus, boron, carbon, aluminum, silicon, tin, germanium, indium, antimony and beryllium, xe2x80x9cixe2x80x9d ranges from about 70 to 87 atom percent and xe2x80x9cjxe2x80x9d ranges from 13 to 30 atom percent. Such materials are conveniently prepared by rapid quenching from the melt using processing techniques that are now wellknown in the art.
Metallic glass alloys substantially lack any long range atomic order and are characterized by x-ray diffraction patterns consisting of diffuse (broad) intensity maxima, qualitatively similar to the diffraction patterns observed for liquids or inorganic oxide glasses. However, upon heating to a sufficiently high temperature, they begin to crystallize with evolution of the heat of crystallization; correspondingly, the x-ray diffraction pattern thereby begins to change from that observed for amorphous to that observed for crystalline materials. Consequently, metallic alloys in the glassy form are in a metastable state. This metastable state of the alloy offers significant advantages over the crystalline form of the alloy, particularly with respect to the mechanical and magnetic properties of the alloy.
Use of metallic glasses in magnetic applications has been disclosed in the ""513 Patent. However, certain combinations of magnetic properties are needed to realize magnetic components required in modern electronics technology. For example, U.S. Pat. No. 5,284,528 issued Feb. 8, 1994 to Hasegawa et al., addresses such a need. One of the important magnetic properties that affect the performance of a magnetic component used in electrical or electronic devices is called magnetic anisotropy. Magnetic materials are in general magnetically anisotropic and the origin of the magnetic anisotropy differs from material to material. In crystalline magnetic materials, one of the crystallographic axes could coincide with the direction of magnetic anisotropy. This magnetically anisotropic direction then becomes the magnetic easy direction in the sense that the magnetization prefers to lie along this direction. Since there are no well-defined crystallographic axes in metallic glass alloys, magnetic anisotropy could be considerably reduced in these materials. This is one of the reasons that metallic glass alloys tend to be magnetically soft, which makes them useful in many magnetic applications. The other important magnetic property is called magnetostriction, which is defined as a fractional change in physical dimension of a magnetic material when the material is magnetized from the demagnetized state. Thus magnetostriction of a magnetic material is a function of applied magnetic field. From a practical standpoint, the term xe2x80x9csaturation magnetostrictionxe2x80x9d (xcexs) is often used. The quantity xcexs is defined as the fractional change in length that occurs in a magnetic material when magnetized along its length direction from the demagnetized to the magnetically saturated state. The value of magnetostriction is thus a dimensionless quantity and is given conventionally in units of microstrain (i.e., a fractional change in length, usually parts per million or ppm).
Magnetic alloys of low magnetostriction are desirable for the following reasons:
1. Soft magnetic properties characterized by low coercivity, high permeability, etc. are generally obtained when both the saturation magnetostriction and the magnetic anisotropy of the material become small. Such alloys are suitable for various soft magnetic applications, especially at high frequencies.
2. When magnetostriction is low and preferably zero, magnetic properties of such near-zero magntostrictive materials are insensitive to mechanical strain. When this is the case, there is little need for stress-relief annealing after winding, punching or other physical handling needed to form a device from such material. In contrast, magnetic properties of stress-sensitive materials are considerably degraded by even small elastic stresses. Such materials must be carefully annealed after the final forming step.
3. When magnetostriction is nearzero, a magnetic material under ac excitation shows a small magnetic loss due to a low coercivity and reduced energy loss by reduced magneto-mechanical coupling via magnetostriction. Core loss of such a near-zero magnetostrictive material can be quite low. Thus, near-zero magnetostrictive magnetic materials are useful where low magnetic loss and high permeability are required. Such applications include a variety of tape-wound and laminated magnetic components such as power transformers, saturable reactors, linear reactors, interface transformers, signal transformers, magnetic recording heads and the like. Electromagnetic devices containing near-zero magnetostrictive materials generate little acoustic noise under ac excitation. While this is the reason for the reduced core loss mentioned above, it is also a desirable characteristic in itself because it reduces considerably the audible hum inherent in many electromagnetic devices.
There are three well-known crystalline alloys of zero or near-zero magnetostriction: Nickel-iron alloys containing approximately 80 atom percent nickel (e.g. xe2x80x9c80 Nickel Permalloysxe2x80x9d); cobalt-iron alloys containing approximately 90 atom percent cobalt; and iron-silicon alloys containing approximately 6.5 wt. percent silicon. Of these alloys, permalloys have been used more widely than the others because they can be tailored to achieve both zero magnetostriction and low magnetic anisotropy. However, these alloys are prone to be sensitive to mechanical shock, which limits their applications. Cobalt-iron alloys do not provide excellent soft magnetic properties due to their strong negative magnetocrystalline anisotropy. Although some improvements have been made recently in producing iron-based crystalline alloys containing 6.5% silicon [J. Appl. Phys. Vol. 64, p.5367 (1988)], wide acceptance of them as a technologically competitive material is yet to be seen.
As mentioned above, magnetocrystalline anisotropy is effectively absent in metallic glass alloys due to the absence of crystal structures. It is, therefore, desirable to seek glassy metals with zero magnetostriction. The above mentioned chemical compositions which led to zero or near-magnetostriction in crystalline alloys were thought to give some clues to this effort. The results, however, were disappointing. To this date, only Co-rich and Co-Ni-based alloys with small amount of iron have shown zero or near-zero magnetostriction in glassy states. Examples for these alloys have been reported for Co72Fe3P16B6Al3 (AIP Conference Proceedings, No. 24, pp.745-746 (1975)) and Co31.2Fe7.8Ni39.0B14Si8 (Proceedings of 3rd International Conference on Rapidly Quenched Metals, p.183 (1979)). Co-rich metallic glass alloys with near-zero magnetostriction are commercially available under the trade names of METGLAS(copyright) alloys 2705M and 2714A (AlliedSignal Inc.) and VITROVAC(copyright) 6025 and 6030 (Vacuumschmelze GmbH). These alloys have been used in various magnetic components operated at high frequencies. Only one alloy (VITROVAC 6006) based on Co-Ni-based metallic glass alloys has been commercially available for anti-theft marker application (U.S. Pat. No. 5,037,494). Clearly desirable are new magnetic metallic glass alloys based on Co and Ni which are magnetically more versatile than the existing alloy.
In accordance with the invention, there is provided a magnetic alloy that is at least 70% glassy and which has a low magnetostriction. The metallic glass alloy has the composition CoaNibFecMdBeSifCg where M is at least one element selected from the group consisting of Cr, Mo, Mn and Nb, xe2x80x9ca-gxe2x80x9d are in atom percent and the sum of xe2x80x9ca-gxe2x80x9d equals 100, xe2x80x9caxe2x80x9d ranges from about 25 to about 60, xe2x80x9cbxe2x80x9d ranges from about 5 to about 45, xe2x80x9ccxe2x80x9d ranges from about 6 to about 12, xe2x80x9cdxe2x80x9d ranges from about 0 to about 3, xe2x80x9cexe2x80x9d ranges from about 5 to 25, xe2x80x9cfxe2x80x9d ranges from about 0 to about 15 and xe2x80x9cgxe2x80x9d ranges from about 0 to 6. The metallic glass alloy has a value of the saturation magnetostriction ranging from about xe2x88x923 to +3 ppm. The metallic glass alloy is cast by rapid solidification from the melt into ribbon or sheet or wire form and is wound or stacked to form a magnetic component. Depending on the need, the magnetic component is heat-treated (annealed) with or without a magnetic field below its crystallization temperature. The resultant magnetic core or component is an inductor with B-H characteristics ranging from a rectangular to a linear type.
Metallic glass alloys heat-treated in accordance with the method of this invention are especially suitable for use in devices operated at high frequencies, such as saturable reactors, linear reactors, power transformers, signal transformers and the like.
Metallic glass alloys of the present invention are also useful as magnetic markers in electronic surveillance systems.